CN103641173A

CN103641173A - Preparation method of graphite alkene like tungsten disulfide nanometer sheet

Info

Publication number: CN103641173A
Application number: CN201310533441.3A
Authority: CN
Inventors: 唐华; 张向华; 李磊; 李长生
Original assignee: Jiangsu University
Current assignee: Jiangsu University
Priority date: 2013-11-04
Filing date: 2013-11-04
Publication date: 2014-03-19
Anticipated expiration: 2033-11-04
Also published as: CN103641173B

Abstract

The invention discloses a preparation method of graphite alkene like tungsten disulfide nanometer sheet, which employs a high temperature solid phase synthesis method, and the method comprises the following steps: mixing thiourea and WO3 according to mol ratio 20:1-41:1 and fully grinding, and containing the grinded powder into a porcelain boat; heating a tubular furnace to 800-900 DEG C and letting nitrogen in; quickly pushing the porcelain boat into a central heat zone position of the tubular furnace and processing for 30-60 min at constant temperature; then, the mixture is naturally cooled to room temperature, and the graphite alkene like tungsten disulfide nanometer sheet is obtained. The invention has the advantages of simple technology and low cost, and the obtained product has high purity and yield, and is hopeful to be used in large scale industrial production.

Description

The preparation method of one kind Graphene tungsten disulfide nano slices

Technical field

The present invention relates to inorganic materials tungsten disulfide (WS ₂) preparation field, that concrete is the preparation method of class Graphene tungsten disulfide nano slices.

Background technology

Graphene is as only having monolayer carbon atomic thickness and being with hexangle type the two-dimensional nano material that honeycomb lattice extends in plane, because it has unique electrical behavior and high specific surface area, become after soccerballene, carbon nanotube by the simple substance carbon family member of extensive concern; Graphene is typical two-dimensional nanostructure system, its thickness is at atomic scale, planar diameter but can reach submillimeter and above size, and the simple substance carbon bill of material that the quantum confined effect that its two-dimentional yardstick height anisotropy shows and surface effects make this individual layer reveals and the distinct electrical behavior of body phase material, mechanical property and optics, thermal property etc.; Be subject to the inspiration of Graphene, people start to pay close attention to the mineral compound that other have two-dimensional layer crystal structure characteristic, as have the transition metal dichalcogenide WS of single layer structure ₂and MoS ₂.

The two dimensional crystal material with " sandwich is sandwich " laminate structure that class Graphene tungsten disulfide is comprised of the single or multiple lift tungsten disulfide of hexagonal system: individual layer tungsten disulfide consists of three layers of atomic shell, middle one deck is tungsten atom layer, the upper and lower two-layer sulphur atom layer that is, tungsten atom layer is by the folded formation class of two-layer sulphur atom layer " sandwich " structure, and tungsten atom and sulphur atom form two-dimentional atomic crystal with covalent bonds; Multilayer tungsten disulfide is comprised of some individual layer tungsten disulfides, is generally no more than five layers, and interlayer exists weak Van der Waals force; " sandwich is sandwich " laminate structure of this uniqueness makes class Graphene tungsten disulfide nano slices gather around and have wide practical use in various fields such as lubricant, catalysis, stored energy, sensor, electroluminescent; In addition, different from the Graphene with two-dimensional layered structure, class Graphene tungsten disulfide also has special energy band structure; Although Graphene has high conductivity at two dimensional surface, because pure grapheme material does not have band gap, for it has brought drawback at electron device as the application in transistor; But class Graphene tungsten disulfide material but shows abundant electrical behavior, has the nature and characteristic different from body phase material; The macroscopic material of tungsten disulfide is that band gap is at the indirect band-gap semiconductor of 1.3 eV, the tungsten disulfide of individual layer is that band gap is the direct band-gap semicondictor of 2.1eV, this special energy band structure, makes class Graphene Wolfram disulfide nano material can be widely used in the preparation of electron device, phototransistor, energy storage device; Yet, general chemistry, Physical are difficult to prepare the class Graphene tungsten disulfide with laminate structure, the method that can adopt at present mainly contains the stripping method of " from top to bottom " such as micromechanical forces stripping method, lithium ion graft process, liquid phase ultrasonic methods, and the synthesis method of high temperature thermolysis, vapour deposition, hydrothermal method etc. " from bottom to top ", the prepared class Graphene tungsten disulfide output of above method is all considerably less, high temperature solid-state method output is high, but does not also have high temperature solid-state method to prepare the report of class Graphene tungsten disulfide nano slices at present.

Summary of the invention

The preparation method who the object of this invention is to provide the preparation class Graphene tungsten disulfide nano slices that a kind of technique is simple, cost is low.

The method of preparing class Graphene tungsten disulfide nano slices of the present invention, employing be high temperature solid-state method, step is as follows: by sulphur source and WO ₃powder in molar ratio 20:1 ~ 41:1 mixes, mixed powder is ground powder is mixed, high temperature process furnances is warmed up to 800-900 ℃, in tube furnace, pass into shielding gas simultaneously, open tube furnace exit end ring flange, powder after grinding is inserted in high temperature process furnances, tighten rapidly ring flange, at 800-900 ℃ of insulation 30-60min, sulphur source pyrolytic decomposition produces dithiocarbonic anhydride and reacts generation tungsten disulfide with tungstic oxide, utilize the high temperature moment vigorous reaction of powder, produce a large amount of gas, the erosion effect of gas causes the separation of stratiform tungsten disulfide nano slices, generate ultrathin nanometer sheet, furnace cooling is to room temperature, obtain class Graphene tungsten disulfide nano slices.

In preparation process of the present invention, all reagent is commerical prod, does not need to prepare again.

Described sulphur source is thiocarbamide.

Described mixed powder is ground and powder mixed refer to that utilizing mortar that mixed powder is ground to 30-60min mixes powder.

Described high temperature process furnances be warmed up to 800-900 ℃ of finger and be warmed up to 800-900 ℃ with the speed of 10 ℃/min.

Described shielding gas is nitrogen.

The cost of the inventive method is inexpensive, and production technique is simple and easy to control, and the nanometer sheet thickness of preparation is thinner, and lateral dimension is larger, and product output capacity is high, is applicable to large-scale industrial production.

Accompanying drawing explanation

Fig. 1 is the XRD spectra of the class Graphene tungsten disulfide nano slices that makes of the present invention.

Fig. 2 is field emission scanning electron microscope (SEM) photo of the class Graphene tungsten disulfide nano slices that makes of the present invention.

Fig. 3 is projection Electronic Speculum (TEM) photo of the class Graphene tungsten disulfide nano slices that makes of the present invention.

Embodiment

Below in conjunction with example, further illustrate the present invention.

Embodiment 1:

By 0.5gWO ₃after mixing with 4.92g thiocarbamide, with mortar, grind 45min, pack the powder after grinding into porcelain boat stand-by; Tube furnace temperature is increased to 850 ℃, in tube furnace, passes into nitrogen; At tube furnace temperature-stable, open tube furnace exit end ring flange during at 850 ℃, porcelain boat is pushed into rapidly to position, tube furnace central thermal zone, insulation 1h; Then after tube furnace naturally cools to room temperature, unload tube furnace two ends ring flange, take out porcelain boat, obtain black powder, i.e. class Graphene tungsten disulfide nano slices.

Embodiment 2:

By 0.5gWO ₃after mixing with 3.3g thiocarbamide, with mortar, grind 30min, pack the powder after grinding into porcelain boat stand-by; Tube furnace temperature is increased to 800 ℃, passes into nitrogen; At tube furnace temperature-stable, open tube furnace exit end ring flange during at 800 ℃, porcelain boat is pushed into rapidly to position, tube furnace central thermal zone, insulation 30min; Then after tube furnace naturally cools to room temperature, obtain black powder, i.e. class Graphene tungsten disulfide nano slices.

Embodiment 3:

By 0.5gWO ₃after mixing with 6.6g thiocarbamide, with mortar, grind 60min, pack the powder after grinding into porcelain boat stand-by; Tube furnace temperature is increased to 900 ℃, passes into nitrogen; At tube furnace temperature-stable, open tube furnace exit end ring flange during at 900 ℃, porcelain boat is pushed into rapidly to position, tube furnace central thermal zone, insulation 60min; Then after tube furnace naturally cools to room temperature, obtain black powder, i.e. class Graphene tungsten disulfide nano slices.

Fig. 1 is the XRD figure spectrum of prepared product, and product is pure WS ₂hexagonal; Fig. 2 is the SEM photo of prepared product, can obviously see that a large amount of ultrathin nanometer sheets generate, and without agglomeration, nanometer sheet thickness is 3-5 nm; Fig. 3 is the TEM photo of prepared product, can see many class graphene nanometer sheets, and the structure of nanometer sheet is homogeneous very, and defect is less.

Claims

1. the preparation method of a kind Graphene tungsten disulfide nano slices, is characterized in that comprising the steps:

By sulphur source and WO ₃powder is mixed in proportion; mixed powder is ground; powder is mixed, high temperature process furnances is warmed up to 800-900 ℃, in tube furnace, pass into shielding gas simultaneously; open tube furnace exit end ring flange; powder after grinding is inserted in high temperature process furnances, tighten rapidly ring flange, at 800-900 ℃ of insulation 30-60min; furnace cooling, to room temperature, obtains class Graphene tungsten disulfide nano slices.

2. according to the preparation method of the kind Graphene tungsten disulfide nano slices described in right 1, it is characterized in that, described sulphur source is thiocarbamide, wherein thiocarbamide and WO ₃the mol ratio of powder is 20:1 ~ 41:1.

3. according to the preparation method of the kind Graphene tungsten disulfide nano slices described in right 1, it is characterized in that, described mixed powder is ground and powder mixed refer to that utilizing mortar that mixed powder is ground to 30-60min mixes powder.

4. according to the preparation method of the kind Graphene tungsten disulfide nano slices described in right 1, it is characterized in that, described high temperature process furnances be warmed up to 800-900 ℃ of finger and be warmed up to 800-900 ℃ with the speed of 10 ℃/min.

5. according to the preparation method of the kind Graphene tungsten disulfide nano slices described in right 1, it is characterized in that, described shielding gas is nitrogen.

6. according to the preparation method of the kind Graphene tungsten disulfide nano slices described in right 1, it is characterized in that, the thickness of described class Graphene tungsten disulfide nano slices is 3 ~ 5nm.